US5356994A - Adhesive/sealant composition comprising a rubber component - Google Patents
Adhesive/sealant composition comprising a rubber component Download PDFInfo
- Publication number
- US5356994A US5356994A US07/909,786 US90978692A US5356994A US 5356994 A US5356994 A US 5356994A US 90978692 A US90978692 A US 90978692A US 5356994 A US5356994 A US 5356994A
- Authority
- US
- United States
- Prior art keywords
- composition
- rubber
- liquid rubber
- adhesive
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 34
- 239000000565 sealant Substances 0.000 title claims abstract description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 18
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 13
- 238000010276 construction Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000004073 vulcanization Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical group 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000005062 Polybutadiene Substances 0.000 description 19
- 239000003921 oil Substances 0.000 description 16
- 229920002857 polybutadiene Polymers 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 239000002318 adhesion promoter Substances 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Chemical group 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000008036 rubber plasticizer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical compound OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- -1 thiurams Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J113/00—Adhesives based on rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
Definitions
- the present invention relates to a hot-vulcanisable, pumpable rubber-based adhesive/sealant suitable for bonding metal sheeting in the construction of automobile shells.
- the bonding of metal sheeting in the construction of automobile shells has the objective of sealing cavities and suppressing any vibration which occur.
- the sheeting used is coated with a number of grams of corrosion-protection oils and drawing oils per square meter, and should be able to absorb these oils.
- the adhesive/sealant is pumped at temperatures of from about 50° to 80° C. and applied to one side of the sheeting to be bonded. The second sheet is then pressed against the first sheet. It should also be ensured here that the second sheet is not applied until the adhesive/sealant applied has cooled and that, nevertheless, good oil absorption and adhesion are achieved.
- the adhesive/sealant must be stable for a relatively long time at the processing temperatures. Curing should not take place at temperatures below from about 150° to 200° C., as are usual in the baking ovens used in automobile production.
- the use of solvent-free, pumpable, rubber-based adhesives/sealant is known, for example in EP-A-0 097 394, where the rubber component comprises a liquid polybutadiene, to which small amounts of solid polybutadiene can be admixed.
- adhesives/sealants do not achieve the good adhesion required in automobile production.
- the term "pumpable” refers to a composition that may be pumped, by means of conventional pumps for hot-melt substances, at elevated temperatures such as about 60° C.
- EP-A-0 256 316 describes adhesives/sealants having a rubber component comprising polybutadiene liquid rubber and chemically depolymerised solid rubber.
- the depolymerisation of the solid rubber is said to give better rheological properties.
- depolymerisation of the solid rubber has the disadvantage of an additional process step.
- DE-A-38 34 818 describes an adhesive/sealant whose rubber component comprises polybutadiene liquid rubber containing terminal hydroxyl groups and cis-1,4-polybutadiene solid rubber.
- DE-A 27 58 222 discloses pressure-sensitive adhesives for self-adhesive tapes containing tackifying resins, for example polyterpenes or polybutene, and a maleic anhydride-modified liquid polybutadiene. Curing is carried out at room temperature by means of polyamines or poly-epoxides.
- EP-A 0 181 441 discloses cold-curing sealants/adhesives which contain, as binders, hydroxyl-containing homopolymers or copolymers of 1,3-butadiene which carry lateral succinic anhydride groups. Curing is carried out using organic nitrogen bases selected from amines and N-alkylimidazoles.
- the object of the invention is now to provide a hot-vulcanisable, pumpable adhesive/sealant for bonding metal sheeting in the construction of automobile shells which has improved overall properties.
- an adhesive/sealant where the rubber component is a mixture of butadiene solid rubber and butadiene or isoprene liquid rubber, characterised in that the liquid rubber contains carboxylic acid groups.
- the butadiene or isoprene liquid rubber also referred to below as polybutadiene oil or polyisoprene oil, present in the adhesive/sealant according to the invention contains carboxylic acid groups, which are preferably in the form of carboxylic anhydride.
- carboxylic acid groups which are preferably in the form of carboxylic anhydride.
- the adhesive/sealant of the invention is a hot-vulcanisable system, where vulcanisation or crosslinking takes place by the reaction of the double bonds of butadiene or isoprene, for example by means of a sulphur/accelerator system, or by means of free-radical initiators, preferably peroxides.
- the carboxylic acid-modified butadiene or isoprene liquid rubbers used according to the invention have a molecular weight M n of from about 500 to 20,000, preferably from about 1,000 to 10,000 and more preferably from about 1,500 to 5,000 and preferably have a viscosity at 20° C. of from 1 to 250 Pa.s.
- liquid rubbers having a high content of cis-1,4 double bonds, preferably more than about 70 mole percent of cis-1,4 double bonds, based on the total double bonds of the molecule, and having not more than about 2 mole percent of vinyl double bonds, based on the total double bonds of the molecule.
- the term vinyl double bond refers to to a unit of a liquid rubber molecule which is polymerized through the double bond in the 1-position, resulting in a vinyl double bond attached to the polymer backbone.
- a vinyl double bond refers to a 1,2-polymerized butadiene in a polybutadiene liquid rubber molecule.
- the polybutadiene of the following formula (I) illustrates such groups, where the unit [x] depicts a cis-1,4 double bond, the unit [y] depicts a trans-1,4 double bond, and the unit [z] depicts a vinyl double bond.
- the carboxylic acid groups of butadiene or isoprene liquid rubber generally contain from 3 to 10, preferably 4 to 6, carbon atoms and are derived, for example, from acrylic acid, methacrylic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or the anhydrides thereof, so long as the acids are able to form anhydrides. They are randomly distributed over the polymer molecule, each polymer molecule containing from 1 to 10, preferably from 2 to 6, carboxylic acid groups or from 1 to 6, preferably from 1 to 3, carboxylic anhydride groups.
- the adhesives/sealants of the invention may also contain, in addition to the carboxylic acid-modified liquid rubber, a non-modified liquid rubber, provided that a 50/50 weight ratio should not be exceeded.
- a non-modified liquid rubber provided that a 50/50 weight ratio should not be exceeded.
- the butadiene solid rubber is suitably either polybutadiene or a butadiene-styrene rubber having a molecular weight M n of from about 50,000 to 500,000, preferably from about 80,000 to 200,000.
- the polybutadiene contains predominantly cis-1,4 double bonds, preferably at least about 95 mole percent of cis-1,4 double bonds, based on the total double bonds of the molecule.
- the styrene-butadiene solid rubber is a random copolymer containing from about 15 to 25 mole percent of styrene.
- the adhesives/sealants of the invention may contain conventional fillers, other additives and processing assistants in conventional amounts.
- suitable fillers are coated calcium carbonate, calcium oxide and carbon black. It is particularly preferred to use a mixture of these three fillers which contains from about 23 to 70% by weight, preferably from about 30 to 60% by weight and in particular from about 50 to 60% by weight, of coated calcium carbonate, from about 1 to 5% by weight, preferably from about 2 to 5% by weight and in particular from about 3 to 5% by weight, of calcium oxide and from about 1 to 10% by weight, preferably from about 1 to 5% by weight and in particular from about 3 to 5% by weight, of carbon black.
- plasticisers may also be used; it is preferred to use paraffinic, aromatic or in particular naphthenic oils.
- the adhesive/sealant of the invention may contain adhesion promoters so long as these do not undergo chemical reactions with the other components of the composition.
- adhesion promoters are phenolic resins and silanes.
- the adhesives/sealants according to the invention are cured by hot vulcanisation at baking temperatures of, for example, from about 150° to 200° C. which are conventional in the construction of automobile shells; it is preferred to use a sulphur/accelerator vulcanisation system, but it is also possible to use free-radical initiators.
- Suitable accelerators are benzothiazoles, thiurams, dithiocarbamates, thioureas or mixtures thereof.
- Benzothiazoles, for example dibenzothiazole disulphide, are preferred.
- thermal free-radical initiators are organic peroxides, in particular those having high decomposition temperatures.
- Preferred examples are dicumyl peroxide and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane.
- Table I below shows the composition of some typical adhesives/sealants according to the invention wherein amounts are expressed as percents by weight of the mixture.
- compositions are prepared in a Pfleiderer compounder. First, the butadiene solid rubber is kneaded with the fillers, the oxidation stabiliser and the plasticiser until the mixture is homogeneous, the carboxylic acid-modified liquid rubber is then added, and finally the vulcanisation chemicals (zinc oxide, sulphur, accelerator and aliphatic carboxylic acid) are incorporated into the composition with cooling.
- vulcanisation chemicals zinc oxide, sulphur, accelerator and aliphatic carboxylic acid
- Oiled steel is used to test the adhesives/sealants.
- the adhesive/sealant is first warmed to a temperature of 60° C. and then applied to the oiled steel sheeting in a bead thickness of 4 mm.
- the second sheet is pressed on, the adhesive/sealant bead is compressed to a layer thickness of 2 mm, and curing is carried out for 30 minutes at a temperature of 180° C.
- the shear strength is measured in accordance with DIN 53281 on a bonded area of 2.5 ⁇ 0.2 cm and the T-peel is measured in accordance with DIN 53283 on a bonded area of 2.5 ⁇ 7.5 ⁇ 0.2 cm.
- the failure mechanism is assessed visually as follows:
- A/C predominantly adhesive, partly cohesive
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4122849 | 1991-07-10 | ||
DE4122849A DE4122849A1 (de) | 1991-07-10 | 1991-07-10 | Kleb/dichtstoff auf kautschukbasis |
Publications (1)
Publication Number | Publication Date |
---|---|
US5356994A true US5356994A (en) | 1994-10-18 |
Family
ID=6435842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/909,786 Expired - Fee Related US5356994A (en) | 1991-07-10 | 1992-07-07 | Adhesive/sealant composition comprising a rubber component |
Country Status (11)
Country | Link |
---|---|
US (1) | US5356994A (de) |
EP (1) | EP0524058B2 (de) |
JP (1) | JPH05194922A (de) |
KR (1) | KR930002473A (de) |
AT (1) | ATE131852T1 (de) |
AU (1) | AU1958192A (de) |
CA (1) | CA2073664A1 (de) |
DE (2) | DE4122849A1 (de) |
DK (1) | DK0524058T3 (de) |
ES (1) | ES2085588T5 (de) |
ZA (1) | ZA924286B (de) |
Cited By (9)
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US5691052A (en) * | 1995-06-07 | 1997-11-25 | American National Can Company | Polymeric compositions with high self-adhesion and packaging materials and packages made therefrom |
US5760135A (en) * | 1992-11-17 | 1998-06-02 | Ralf Korpman Associates, Inc. | Pressure sensitive adhesive |
US6204321B1 (en) | 1993-12-17 | 2001-03-20 | Henkel Corporation | Sealant and adhesive with damping properties |
US6361643B2 (en) | 1994-11-23 | 2002-03-26 | Henkel Teroson Gmbh | Method for reducing mechanical vibration in metal constructions |
USH2047H1 (en) | 1999-11-10 | 2002-09-03 | Henkel Corporation | Reinforcement laminate |
US6448338B1 (en) | 1997-07-16 | 2002-09-10 | Henkel Teroson Gmbh | Hot-setting wash-fast sealant for shell structures |
US20070128931A1 (en) * | 2005-12-05 | 2007-06-07 | Ziwei Liu | Polyester gel adapted for use with polycarbonate components |
US20140202608A1 (en) * | 2013-01-18 | 2014-07-24 | Paul Harry Sandstrom | Rubber cement and tire with fabricated tire tread |
CN113950503A (zh) * | 2019-10-02 | 2022-01-18 | 住友橡胶工业株式会社 | 橡胶组合物和轮胎 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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DE4441656A1 (de) * | 1994-11-23 | 1996-05-30 | Teroson Gmbh | Elastomerprodukte mit akustischen Dämpfungseigenschaften |
DE19502381A1 (de) * | 1995-01-26 | 1996-08-01 | Teroson Gmbh | Strukturelle Rohbauklebstoffe auf Kautschukbasis |
DE19652455C2 (de) * | 1995-12-20 | 2000-04-13 | Spiess Kunststoff Recycling | Verfahren zur Aufbereitung von Feuchtigkeit enthaltendem Kunststoff-Recycling-Material, Verfahren zur Herstellung von Fertigprodukten und Gegenstände aus Kunststoff-Recycling-Material |
DE19914071A1 (de) * | 1999-03-27 | 2000-10-19 | Oskar Fleck | Plastisch verformbares Abdeckmaterial |
DE10062859A1 (de) * | 2000-12-16 | 2002-06-27 | Henkel Teroson Gmbh | Mehrschichtige Verbundmaterialien mit organischen Zwischenschichten auf Kautschukbasis |
DE102005003057A1 (de) | 2005-01-22 | 2006-07-27 | Henkel Kgaa | Spritzbare, niedrigviskose Kautschuk-Dämpfungsmassen |
JP5228419B2 (ja) * | 2007-09-14 | 2013-07-03 | 住友ベークライト株式会社 | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP5228443B2 (ja) * | 2007-10-30 | 2013-07-03 | 住友ベークライト株式会社 | 樹脂組成物及び樹脂組成物を使用して作製した半導体装置 |
JP6198574B2 (ja) * | 2013-10-30 | 2017-09-20 | 株式会社クラレ | 粘着剤組成物 |
DE102014003874A1 (de) * | 2014-03-19 | 2015-09-24 | Leoni Kabel Holding Gmbh | Klebstoff |
JP7273718B2 (ja) | 2017-10-05 | 2023-05-15 | 株式会社クラレ | 変性液状ジエン系ゴム |
US10526473B2 (en) | 2018-04-11 | 2020-01-07 | Fina Technology, Inc. | Curable liquid rubber compositions and methods of manufacturing the same |
JP7049732B1 (ja) * | 2022-02-01 | 2022-04-07 | イイダ産業株式会社 | マスチック接着剤組成物 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925272A (en) * | 1972-03-18 | 1975-12-09 | Asahi Chemical Ind | Composite elastomer compositions |
US4451615A (en) * | 1980-05-09 | 1984-05-29 | Loctite (Ireland) Limited | Polyisoprene toughened adhesive composition |
US4600745A (en) * | 1982-06-17 | 1986-07-15 | Evode Limited | Adhesive compositions |
CA1248271A (en) * | 1984-10-05 | 1989-01-03 | Klaus Gorke | Heat cross-linkable polymer compositions and their production process |
US4824512A (en) * | 1986-07-24 | 1989-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Low viscosity, pregelable rubber-based adhesives |
-
1991
- 1991-07-10 DE DE4122849A patent/DE4122849A1/de not_active Ceased
-
1992
- 1992-06-11 ZA ZA924286A patent/ZA924286B/xx unknown
- 1992-07-07 US US07/909,786 patent/US5356994A/en not_active Expired - Fee Related
- 1992-07-08 EP EP92401967A patent/EP0524058B2/de not_active Expired - Lifetime
- 1992-07-08 JP JP4180699A patent/JPH05194922A/ja active Pending
- 1992-07-08 DK DK92401967.2T patent/DK0524058T3/da active
- 1992-07-08 DE DE69206906T patent/DE69206906T3/de not_active Expired - Lifetime
- 1992-07-08 AT AT92401967T patent/ATE131852T1/de not_active IP Right Cessation
- 1992-07-08 ES ES92401967T patent/ES2085588T5/es not_active Expired - Lifetime
- 1992-07-09 KR KR1019920012196A patent/KR930002473A/ko not_active Application Discontinuation
- 1992-07-09 AU AU19581/92A patent/AU1958192A/en not_active Abandoned
- 1992-07-10 CA CA002073664A patent/CA2073664A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925272A (en) * | 1972-03-18 | 1975-12-09 | Asahi Chemical Ind | Composite elastomer compositions |
US4451615A (en) * | 1980-05-09 | 1984-05-29 | Loctite (Ireland) Limited | Polyisoprene toughened adhesive composition |
US4600745A (en) * | 1982-06-17 | 1986-07-15 | Evode Limited | Adhesive compositions |
CA1248271A (en) * | 1984-10-05 | 1989-01-03 | Klaus Gorke | Heat cross-linkable polymer compositions and their production process |
US4824512A (en) * | 1986-07-24 | 1989-04-25 | Henkel Kommanditgesellschaft Auf Aktien | Low viscosity, pregelable rubber-based adhesives |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5760135A (en) * | 1992-11-17 | 1998-06-02 | Ralf Korpman Associates, Inc. | Pressure sensitive adhesive |
US6204321B1 (en) | 1993-12-17 | 2001-03-20 | Henkel Corporation | Sealant and adhesive with damping properties |
US6361643B2 (en) | 1994-11-23 | 2002-03-26 | Henkel Teroson Gmbh | Method for reducing mechanical vibration in metal constructions |
US5691052A (en) * | 1995-06-07 | 1997-11-25 | American National Can Company | Polymeric compositions with high self-adhesion and packaging materials and packages made therefrom |
US6448338B1 (en) | 1997-07-16 | 2002-09-10 | Henkel Teroson Gmbh | Hot-setting wash-fast sealant for shell structures |
USH2047H1 (en) | 1999-11-10 | 2002-09-03 | Henkel Corporation | Reinforcement laminate |
US20070128931A1 (en) * | 2005-12-05 | 2007-06-07 | Ziwei Liu | Polyester gel adapted for use with polycarbonate components |
US20140202608A1 (en) * | 2013-01-18 | 2014-07-24 | Paul Harry Sandstrom | Rubber cement and tire with fabricated tire tread |
US9133371B2 (en) * | 2013-01-18 | 2015-09-15 | The Goodyear Tire & Rubber Company | Rubber cement and tire with fabricated tire tread |
CN113950503A (zh) * | 2019-10-02 | 2022-01-18 | 住友橡胶工业株式会社 | 橡胶组合物和轮胎 |
CN113950503B (zh) * | 2019-10-02 | 2023-08-01 | 住友橡胶工业株式会社 | 橡胶组合物和轮胎 |
Also Published As
Publication number | Publication date |
---|---|
AU1958192A (en) | 1993-01-14 |
DK0524058T3 (da) | 1996-07-01 |
CA2073664A1 (en) | 1993-01-11 |
DE69206906T2 (de) | 1997-04-17 |
DE4122849A1 (de) | 1993-01-14 |
JPH05194922A (ja) | 1993-08-03 |
DE69206906D1 (de) | 1996-02-01 |
EP0524058B1 (de) | 1995-12-20 |
ZA924286B (en) | 1993-03-31 |
DE69206906T3 (de) | 2004-06-03 |
EP0524058B2 (de) | 2003-08-27 |
ES2085588T3 (es) | 1996-06-01 |
ATE131852T1 (de) | 1996-01-15 |
KR930002473A (ko) | 1993-02-23 |
EP0524058A1 (de) | 1993-01-20 |
ES2085588T5 (es) | 2004-05-16 |
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Owner name: BOSTIK, INC., MASSACHUSETTS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KOCH, MARKUS;REEL/FRAME:006215/0883 Effective date: 19920723 |
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Effective date: 19981018 |
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